Poly[bis­(1-carbamoylguanidinium) [tri-μ-chlorido-dichloridobismuthate(III)]]

Ferjani, H.; Boughzala, H.; Driss, A.

doi:10.1107/S1600536812015668

metal-organic compounds

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doi:10.1107/S1600536812015668

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Poly[bis(1-carbamoylguanidinium) [tri-μ-chlorido-dichloridobismuthate(III)]]

Hel Ferjani,^a Habib Boughzala ^a ^* and Ahmed Driss ^a

^aLaboratoire de Cristallochimie et des Materiaux, Faculté des Sciences de Tunis, Tunisia
^*Correspondence e-mail: habib.boughzala@ipein.rnu.tn

(Received 13 March 2012; accepted 10 April 2012; online 18 April 2012)

The structure of the title organic–inorganic hybrid compound, {(C₂H₇N₄O)₂[BiCl₅]}_n, consists of corrugated chains parallel to [100] of corner-joined [BiCl₆] octahedra, separated by layers of organic 1-carbamoylguanidinum cations. The crystal cohesion is achieved by N—H⋯O and N—H⋯Cl hydrogen bonds, which link the organic and inorganic parts of the structure.

Related literature

For bismuth(III) halide organic–inorganic hybrid compounds, see: Masmoudi et al. (2011 ); Fisher & Norman (1994 ); Samet et al. (2010 ); Papavassiliou et al. (1995 ); Mousdis et al. (1998 ); Rhandour et al. (2011 ). For structures with similar guanidunium cations, see: Bremner & Harrison (2002 , 2003 ); Ritchie & Harrison (2003 ).

Experimental

Crystal data

(C₂H₇N₄O)₂[BiCl₅]
M_r = 592.46
Orthorhombic, P n m a
a = 7.3795 (8) Å
b = 20.706 (4) Å
c = 11.028 (2) Å
V = 1685.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 11.27 mm⁻¹
T = 298 K
0.53 × 0.25 × 0.17 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.048, T_max = 0.094
2612 measured reflections
1880 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.018
2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.10
1880 reflections
98 parameters
H-atom parameters not refined
Δρ_max = 3.03 e Å⁻³
Δρ_min = −1.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.86	2.61	3.271 (8)	135
N1—H1B⋯Cl2ⁱⁱ	0.86	2.50	3.329 (7)	162
N2—H2⋯Cl4ⁱⁱ	0.86	2.70	3.524 (7)	160
N3—H3A⋯Oⁱⁱⁱ	0.86	2.21	3.053 (8)	167
N3—H3B⋯O	0.86	2.08	2.734 (8)	132
N4—H4A⋯Cl1^iv	0.86	2.53	3.347 (7)	160
N4—H4B⋯Cl4ⁱⁱ	0.86	2.59	3.421 (7)	162
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z; (iii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812015668/bg2453sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015668/bg2453Isup2.hkl

checkCIF report

Comment top

Recently there has been considerable interest in bismuth (III) halide organic-inorganic hybrid compounds due to their diverse electrical and optical proprieties, as well as their excellent film process ability (Masmoudi et al., 2011; Fisher & Norman, 1994; Samet et al., 2010; Papavassiliou et al., 1995; Mousdis et al., 1998; Rhandour et al., 2011). In particular, the family of bismuth chlorine-based crystals are self-organized low-dimensional nanostructures to form one-,two- or three dimensional networks where BiCl₆ octahedra can be joined by corners, edges or faces.

We report in this work the synthesis and the structural investigations of the organic-inorganic one-dimensional hybrid compound; Bis(1-carbamoylguanidinum)pentachlorobismuthate(III): [C₂H₇N₄O]₂[BiCl₅]. We note that this material was prepared by slow evaporation at room temperature of an aqueous solution containing Bismuth(III) chloride, cyanoguanidine and chlorhydric acid. The abscence of cyanoguanidine in the synthesis result is probably due to their protonation by the chlorhydric acid, giving the 1-carbamoylguanidine cation (protonated guanidineurea or guanylurea).

As shown in Figure 1, the inorganic backbone is stacked as zigzag chains of BiCl₆ octahedra joined by corner sharing and running along the a axis. Organic cations ([C₂H₇N₄O]₂)²⁺ are located around the inorganic ribbons. Within the BiCl₆ octahedra the bond lengths around Bi range from 2.546 (3) to 2.880 (3) Å which indicate the dominant ionic character of the Bi—Cl bonds in the inorganic framework. In spite of the notable deviation of the bond angles Cl—Bi—Cl from ideal values of 90° and 180°, the octahedral coordination of bismuth reveals the unstereochemical activity of Bi(III) 6s² lone pair electrons.

The 1-carbamoylguanidinium cations ([C₂H₇N₄O]₂)²⁺ are approximately parallel to each other (distanced by 3.574 (3) Å), located around the inorganic chains and form stacks oriented along the a axis. These planar cations (r.m.s. deviation = 0.0178) have a typical geometrical parameters [d_av(N—C)= 1.322 Å] as shown in Fig 2, this situation was previously observed in homologous materials involving guanidunium [C₂H₇N₄O] cations (Bremner & Harrison, 2002; Bremner & Harrison, 2003; Ritchie & Harrison, 2003). Strong N—H···Cl hydrogen bonds link the organic part to the inorganic moiety assuming the crystal cohesion.

Related literature top

For bismuth (III) halide organic–inorganic hybrid compounds, see: Masmoudi et al. (2011); Fisher & Norman (1994); Samet et al. (2010); Papavassiliou et al. (1995); Mousdis et al. (1998); Rhandour et al. (2011). For structures with similar guanidunium cations, see: Bremner & Harrison (2002, 2003); Ritchie & Harrison (2003).

Experimental top

Bismuth chloride BiCl₃ and Cyanoguanidine (C₂H₄N₄) (molar ratio 1:2) was dissolved in 20 ml of absolute ethanol with excess of HCl (to improve solubility). The mixture was stirred then kept at room temperature. Three months later, colorless single crystals were obtained and isolated from the reaction. A suitable single-crystal was selected for the structural determination. Supplementary data for this paper are available from the IUCR electronic archives (CCDC number: 866174).

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The layred structure of (C₂H₇N₄O)₂BiCl₅ build up from organic layers, separated by the inorganic 1-D corner-sharing (BiCl₅)^2- octahedra and showing the N—H···Cl hydrogen bonding (dashed lines).
	Fig. 2. View of the [C₂H₇N₄O]₂[BiCl₅] with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. N-H..O bonds have been omitted for clarity. Symmetry codes: (i): x, 0.5-y, z; (ii): -0.5+x, 0.5-y, 1.5-z ; (iii): 0.5+x, 0.5-y, 1.5-z ;(iv): 0.5+x, y, 1.5-z ; (v): 0.5+x, 0.5-y, 0.5-z ; (vi):0.5+x, y, 0.5-z ;(vii): x, y, -1+z.

Poly[bis(1-carbamoylguanidinium) [tri-µ-chlorido-dichloridobismuthate(III)]] top

Crystal data top

(C₂H₇N₄O)₂[BiCl₅]	F(000) = 1112
M_r = 592.46	D_x = 2.335 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 7.3795 (8) Å	θ = 11–15°
b = 20.706 (4) Å	µ = 11.27 mm⁻¹
c = 11.028 (2) Å	T = 298 K
V = 1685.1 (5) Å³	Prism, colourless
Z = 4	0.53 × 0.25 × 0.17 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.018
Graphite monochromator	θ_max = 27.0°, θ_min = 2.1°
Non–profiled ω/2θ scans	h = −1→9
Absorption correction: ψ scan (North et al., 1968)	k = −2→26
T_min = 0.048, T_max = 0.094	l = −1→14
2612 measured reflections	2 standard reflections every 120 min
1880 independent reflections	intensity decay: 5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters not refined
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0464P)² + 4.6267P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
1880 reflections	Δρ_max = 3.03 e Å⁻³
98 parameters	Δρ_min = −1.73 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (2)

Crystal data top

(C₂H₇N₄O)₂[BiCl₅]	V = 1685.1 (5) Å³
M_r = 592.46	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.3795 (8) Å	µ = 11.27 mm⁻¹
b = 20.706 (4) Å	T = 298 K
c = 11.028 (2) Å	0.53 × 0.25 × 0.17 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.018
T_min = 0.048, T_max = 0.094	2 standard reflections every 120 min
2612 measured reflections	intensity decay: 5%
1880 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.080	H-atom parameters not refined
S = 1.10	Δρ_max = 3.03 e Å⁻³
1880 reflections	Δρ_min = −1.73 e Å⁻³
98 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Bi	0.62878 (4)	0.2500	0.56736 (2)	0.02190 (13)
Cl1	0.6373 (2)	0.38017 (8)	0.56635 (13)	0.0404 (4)
Cl2	0.9594 (3)	0.2500	0.7064 (2)	0.0449 (5)
Cl3	0.3456 (3)	0.2500	0.4355 (2)	0.0405 (5)
Cl4	0.8594 (3)	0.2500	0.3856 (2)	0.0388 (5)
C1	0.1598 (8)	0.4240 (3)	0.5363 (6)	0.0334 (13)
C2	0.1179 (8)	0.4174 (3)	0.3141 (6)	0.0338 (13)
O	0.2300 (8)	0.4830 (3)	0.5350 (5)	0.0581 (14)
N1	0.1374 (9)	0.3932 (3)	0.6381 (6)	0.0543 (17)
H1A	0.1681	0.4111	0.7054	0.065*
H1B	0.0918	0.3550	0.6381	0.065*
N2	0.1010 (8)	0.3947 (3)	0.4317 (4)	0.0376 (13)
H2	0.0473	0.3581	0.4402	0.045*
N3	0.1813 (7)	0.4699 (2)	0.2905 (5)	0.0326 (11)
H3A	0.1882	0.4825	0.2163	0.039*
H3B	0.2194	0.4946	0.3479	0.039*
N4	0.0551 (9)	0.3755 (3)	0.2320 (5)	0.0490 (15)
H4A	0.0580	0.3851	0.1562	0.059*
H4B	0.0118	0.3389	0.2550	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi	0.02407 (18)	0.02518 (17)	0.01645 (17)	0.000	0.00075 (11)	0.000
Cl1	0.0613 (11)	0.0279 (7)	0.0319 (8)	−0.0047 (7)	−0.0009 (7)	0.0008 (5)
Cl2	0.0457 (13)	0.0501 (12)	0.0388 (12)	0.000	−0.0197 (11)	0.000
Cl3	0.0327 (11)	0.0473 (13)	0.0416 (13)	0.000	−0.0128 (9)	0.000
Cl4	0.0432 (12)	0.0433 (11)	0.0300 (11)	0.000	0.0137 (9)	0.000
C1	0.034 (3)	0.036 (3)	0.030 (3)	0.000 (2)	0.004 (3)	0.002 (3)
C2	0.035 (3)	0.035 (3)	0.031 (3)	0.002 (2)	0.007 (2)	−0.003 (2)
O	0.065 (4)	0.049 (3)	0.060 (3)	−0.005 (3)	−0.003 (3)	0.002 (3)
N1	0.071 (4)	0.058 (4)	0.033 (3)	−0.015 (3)	−0.005 (3)	0.010 (3)
N2	0.052 (3)	0.028 (3)	0.033 (3)	−0.008 (2)	0.003 (2)	0.0019 (19)
N3	0.049 (3)	0.027 (2)	0.022 (2)	−0.010 (2)	0.003 (2)	0.007 (2)
N4	0.071 (4)	0.047 (3)	0.029 (3)	−0.017 (3)	0.008 (3)	−0.007 (2)

Geometric parameters (Å, º) top

Bi—Cl3	2.546 (3)	C2—N3	1.213 (8)
Bi—Cl4	2.630 (2)	C2—N4	1.337 (8)
Bi—Cl1ⁱ	2.6961 (17)	C2—N2	1.384 (8)
Bi—Cl1	2.6962 (17)	N1—H1A	0.8600
Bi—Cl2ⁱⁱ	2.791 (2)	N1—H1B	0.8600
Bi—Cl2	2.881 (3)	N2—H2	0.8600
Cl2—Biⁱⁱⁱ	2.791 (2)	N3—H3A	0.8600
C1—N1	1.302 (9)	N3—H3B	0.8600
C1—O	1.327 (8)	N4—H4A	0.8600
C1—N2	1.373 (8)	N4—H4B	0.8600

Cl3—Bi—Cl4	95.50 (10)	N1—C1—N2	117.9 (6)
Cl3—Bi—Cl1ⁱ	90.96 (4)	O—C1—N2	121.4 (6)
Cl4—Bi—Cl1ⁱ	88.95 (3)	N3—C2—N4	124.7 (6)
Cl3—Bi—Cl1	90.96 (4)	N3—C2—N2	122.7 (6)
Cl4—Bi—Cl1	88.95 (4)	N4—C2—N2	112.6 (5)
Cl1ⁱ—Bi—Cl1	177.28 (8)	C1—N1—H1A	120.0
Cl3—Bi—Cl2ⁱⁱ	98.22 (9)	C1—N1—H1B	120.0
Cl4—Bi—Cl2ⁱⁱ	166.28 (8)	H1A—N1—H1B	120.0
Cl1ⁱ—Bi—Cl2ⁱⁱ	90.81 (3)	C1—N2—C2	127.5 (6)
Cl1—Bi—Cl2ⁱⁱ	90.81 (3)	C1—N2—H2	116.3
Cl3—Bi—Cl2	177.32 (7)	C2—N2—H2	116.3
Cl4—Bi—Cl2	81.82 (10)	C2—N3—H3A	120.0
Cl1ⁱ—Bi—Cl2	88.99 (4)	C2—N3—H3B	120.0
Cl1—Bi—Cl2	88.99 (4)	H3A—N3—H3B	120.0
Cl2ⁱⁱ—Bi—Cl2	84.47 (6)	C2—N4—H4A	120.0
Biⁱⁱⁱ—Cl2—Bi	148.77 (10)	C2—N4—H4B	120.0
N1—C1—O	120.6 (7)	H4A—N4—H4B	120.0

Symmetry codes: (i) x, −y+1/2, z; (ii) x−1/2, y, −z+3/2; (iii) x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱⁱ	0.86	2.61	3.271 (8)	135
N1—H1B···Cl2^iv	0.86	2.50	3.329 (7)	162
N2—H2···Cl4^iv	0.86	2.70	3.524 (7)	160
N3—H3A···O^v	0.86	2.21	3.053 (8)	167
N3—H3B···O	0.86	2.08	2.734 (8)	132
N4—H4A···Cl1^vi	0.86	2.53	3.347 (7)	160
N4—H4B···Cl4^iv	0.86	2.59	3.421 (7)	162

Symmetry codes: (ii) x−1/2, y, −z+3/2; (iv) x−1, y, z; (v) −x+1/2, −y+1, z−1/2; (vi) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₂H₇N₄O)₂[BiCl₅]
M_r	592.46
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	7.3795 (8), 20.706 (4), 11.028 (2)
V (Å³)	1685.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	11.27
Crystal size (mm)	0.53 × 0.25 × 0.17

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.048, 0.094
No. of measured, independent and observed [I > 2σ(I)] reflections	2612, 1880, 1596
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.10
No. of reflections	1880
No. of parameters	98
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	3.03, −1.73

Computer programs: CAD-4 EXPRESS (Duisenberg, 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.607	3.271 (8)	134.77
N1—H1B···Cl2ⁱⁱ	0.86	2.499	3.329 (7)	162.41
N2—H2···Cl4ⁱⁱ	0.86	2.702	3.524 (7)	160.39
N3—H3A···Oⁱⁱⁱ	0.86	2.21	3.053 (8)	167
N3—H3B···O	0.86	2.08	2.734 (8)	132
N4—H4A···Cl1^iv	0.86	2.525	3.347 (7)	160.30
N4—H4B···Cl4ⁱⁱ	0.86	2.594	3.421 (7)	161.75

Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1, y, z; (iii) −x+1/2, −y+1, z−1/2; (iv) x−1/2, y, −z+1/2.

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